JPS60184083A - Phthalocyanine compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (Pc is phthalocyanine residue; L is alkylene; R is H, or lower alkyl; n is >=1 integer). EXAMPLE:Co-3,3,3'',3'''-Tetracarboxyphthalocyanine. USE:A high active material. Useful as a monomer having high solubility and compatibility, polymerizable and crosslinkable by electron rays, ultraviolet rays, etc. PREPARATION:A phthalocyanine containing n, usually 2-8 carboxyl groups on the benzene ring, is synthesized by a conventional procedure, and reacted with thionyl chloride, to obtain an acid chloride. Then this compound is reacted with a compound shown by the formula II under heating, to give a compound shown by the formula I .

Description

[Detailed description of the invention] Background of the invention Technical field The present invention relates to novel 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, 30 1480 1981. They have found that it can be easily formed into films, etc., and can be used as 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 F-rays, ultraviolet rays, etc., it could become a highly functional material with an even wider range of uses. It seems likely that this will come true.

++ Purpose of the Invention The purpose 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.

Such objective 1-1 can be achieved by the present invention as described below.

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

Formula %Formula %) (]-In the formula, Pc represents a phthalocyanine residue, L represents an alkylene group, R represents hydrogen or a lower alkyl group, and n is an integer north of l.) ■ Invention Specific Configuration The specific configuration of the present invention will now be described in detail.

In the above formula, L represents an alkylene group, and the alkylene group may be linear or branched. There is no particular limit to the number of carbon atoms,
It may be about 30 or less, usually about 1 to 5, especially about 2 to 3.

R is also hydrogen or a lower alkyl group, especially hydrogen or a methyl group.

Further, n is an integer greater than or equal to 1, 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 more monovalent residue of phthalocyanine; It binds to the Hensen ring forming .

In this case, the vinyl-containing group is bonded to the 3- or 4-position of the Hensen ring of the phthalocyanine, but is usually bonded to the 3- or 4-position.

Therefore, when n=2, the bonding position of the vinyl-containing group is 3.
3'-13,4'-13,3''-13,4''-,4,4
'-, and is a compound of 14 of these isomers.

Also, when n=4, 3, 3', 3", 3"'
- is 1", and when n=8, 3, 4.3', 4', 3"
, 4″, 3″′, 4″′);

Furthermore, there are no particular restrictions on the central atom of phthalocyanine, and in addition to Fe, Cu, Co, and Ni, V, Pb, and Si
, Ge, Sn, AU.

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

In this case, l=T of the phthalocyanine ring may be further coordinated with other ligands.

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

Or Cu is suitable.

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, when n=2, P2O3, n
=4 is Makromol, Chem.

182 2429-2438 (1981), n=8 Makromol, Chefil, l 81 5
, 6 5 (1980).

Next, thionyl chloride is added to this, refluxed, and the precipitate is filtered off and washed with petroleum ether to obtain acid chloride.

To this, CH2=　C-COU-L　-OHR・ (L and R are as above) Add and heat to carry out the reaction.

After the reaction, centrifuge and add water to the supernatant] 7. Quilt the precipitate, filter it, dry it, dissolve it in acetone, concentrate, and then purify.

The phthalocyanine compound 1 thus obtained is, of course, almost the same as the phthalocyanine itself.
It is.

In addition, in the infrared absorption spectrum, 1720 cm-' I
T! ν after f and ν of about 1610-1650 cm-' C=0 degree.

C=C And the melting point is generally 170~2'OO'(
! It decomposes thermally to a certain degree.

■ Specific Effects of the Invention The phthalocyanine compound of the present invention has high solubility in solvents, and dissolves extremely well in organic solvents such as chloroform, benzene, toluene, dioxane, dimethylform J1 amide, and methyl ethyl ketone6. It also has extremely high compatibility with resins such as epoxy resins, vinyl chloride-vinyl acetate copolymers, polyurethane resins, etc. 6 And because it has a vinyl-containing group, especially an acryloyl group or a methacryloyl group, it is highly compatible with electron beams, ultraviolet rays, and X-rays. It can be easily polymerized or crosslinked by, for example,

Therefore, after being formed into a coating film, it can be polymerized or crosslinked to form a recording film for an optical recording medium, etc., and is extremely useful in practice.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown, and the invention and the invention will be explained in further detail.

Example 1 Co-3゜3',3
″,3″′-Tei-racarpoxyphthalocyanine was obtained.

To this was added thionyl 11ide 5OC12, and the mixture was refluxed for 10 hours. The precipitate was filtered, washed with petroleum ether, and Co-3
, 3', 3'', 3'''-tetrofluorinated carbonyl phdalocyanine was obtained.

Consolidation: 196% 20mM of 2-hydroxystyl methacrylate was added to 05g of this acid chloride 9I, and the mixture was reacted at 60°C for 511 hours.

After the reaction, this was centrifuged and -1- water was added to the clear solution to obtain Precipitate V.

Precipitate V was filtered off, dried, and then dissolved in acetin.

This acetone solution was concentrated and opened using acetone as a solvent in a column packed with Wako-Ke yC'-200 (1).

- The developed and separated acetate solution was concentrated and dried to form a blue-green Co-Pc moiety C00CH2CI-120COC (CH3
) = CH2) 40.14 g was obtained.

Yield 17.5% Elemental analysis (%) p Month y Found 57.18 4.07 B, 82 Cafe
, 80,28 4.02 9.37 peoplemaw 613
~618nI11 (ε=10,000) shoulder
670nm (ε=9,000)νc=o, 17
2 FIICII+-'pc=c 1640 cm-' Pyrolysis at 170°C Example 2 In Example 1, Fe-3,3',3''.

A similar synthesis was carried out using 3'''-tetracarboxyphthalocyanine as a raw material.

Yield 12.7% Elemental analysis (%) p Slow y Found 513.97 B, 77 8.92 Cal
c, H, 414,039, 40 people wax 644 n
m (q = 11,200) shoulder - 680n intestine (
ε= 7.800) νc=o 1720cm+-'yC; C1640°1. l-+ Pyrolysis at 170°C.

Yield 12.7% Example 3 In Example 1, the phthalocyanine raw material was Co-3,
3', 3'', 3'''-tetracarboxyphthalocyanine, Ni-3,3', 3'', 3''''-tetracarboxyphthalocyanine, Cu-3,3', 3'', 3'''-tetracarboxyphthalocyanine, The compounds shown in Table 1 below were obtained by replacing CO-dicarboxyphthalocyanine and by replacing the vinyl group-containing raw material with 2-hydroxyethyl acrylate and 2-hydroxy-1-propyl methacrylate.

The elemental analysis values of each compound are also listed in Table 1. In this case, the value in parentheses is the calculated value.

Note that the infrared spectrum is almost the same as above, and
The TRI optical absorption spectrum was almost the same as that of each raw material phthalocyanine.

Further, as a result of differential thermal Tenbin analysis of each of these compounds, thermal decomposition started at 170 to 200°C.

Claims (1)

[Claims] (1) A phthalocyanine compound characterized by being represented by the following formula: Formula % Formula %) (1. In the warm formula, Pc represents a phthalocyanine residue, L represents an alkylene group, R represents hydrogen or a lower alkyl group, and n is an integer from 1 to 1-.)